CN109599571B - Dendritic PtPdCu nano-particle for electrocatalytic oxygen reduction and preparation method thereof - Google Patents

Dendritic PtPdCu nano-particle for electrocatalytic oxygen reduction and preparation method thereof Download PDF

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CN109599571B
CN109599571B CN201710949578.5A CN201710949578A CN109599571B CN 109599571 B CN109599571 B CN 109599571B CN 201710949578 A CN201710949578 A CN 201710949578A CN 109599571 B CN109599571 B CN 109599571B
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邓意达
张媛
胡文彬
张金凤
钟澄
韩晓鹏
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Abstract

本发明提供用于电催化氧还原的枝状PtPdCu纳米颗粒及其制备方法，将钯盐与一定浓度的盐酸按一定比例混合，得到钯前驱体溶液；其次，称取一定量的丹宁酸，按顺序滴入钯前驱体溶液，氯化铜溶液，氯铂酸溶液和去离子水。再将混合物在室温下连续搅拌一定时间后转移到不锈钢高压反应釜中，将水热反应后的产物通过离心清洗，得到枝状PtPdCu纳米颗粒。本发明操作简单方便、可重复性高、成分可控，制备的枝状纳米颗粒具有优异的电催化氧还原性能。

Figure 201710949578

The invention provides dendritic PtPdCu nanoparticles for electrocatalytic oxygen reduction and a preparation method thereof. The palladium salt is mixed with a certain concentration of hydrochloric acid in a certain proportion to obtain a palladium precursor solution; secondly, a certain amount of tannin is weighed, Palladium precursor solution, cupric chloride solution, chloroplatinic acid solution and deionized water were dropped in order. Then, the mixture was continuously stirred at room temperature for a certain period of time and then transferred to a stainless steel autoclave, and the product after the hydrothermal reaction was washed by centrifugation to obtain dendritic PtPdCu nanoparticles. The method has the advantages of simple and convenient operation, high repeatability and controllable components, and the prepared dendritic nanoparticles have excellent electrocatalytic oxygen reduction performance.

Figure 201710949578

Description

Dendritic PtPdCu nano-particle for electrocatalytic oxygen reduction and preparation method thereof
Technical Field
The invention relates to the field of new energy functional materials, in particular to a preparation method of an electrocatalytic oxygen reduction catalyst with simple process, easy operation and good repeatability.
Background
It is well known that proton exchange membrane fuel cells are constrained by the kinetic limitations of the cathodic oxygen reduction reaction, and platinum catalysts are currently the most effective materials for catalyzing oxygen reduction reactions, however, due to the low abundance and high price of platinum in the earth's crust, the widespread use of platinum in fuel cells is limited. Thus platinum-based catalysts are a very promising catalyst option that can replace pure platinum or even be better than it in some catalytic reactions. Therefore, the preparation of nano platinum-based particles having high catalytic activity is a current research focus. Due to the intermetallic synergy (geometric effect and electronic effect), the introduction of other metals becomes the first choice for enhancing the catalytic performance of the catalyst.
At present, noble metal particles are synthesized mainly by a template method, an electrodeposition method, a chemical reduction method, and the like. The template method generally needs to prepare a template in an early stage, remove the template in a later stage and the like, and is easy to cause the damage of the particle morphology in the template removing process, and the process is complicated and the operation is complex. The noble metal prepared by the electrodeposition method has larger particle size, generally in micron level or micron/nanometer level, and the process is difficult to control and has poor repeatability. In contrast, the chemical reduction method has the advantages of simple process, easy operation, easy control of the shape and size of the product, good repeatability and especially obvious advantage of one-step synthesis at lower temperature. Therefore, the nano platinum-based catalysts with various shapes are prepared by adopting a simple chemical reduction method at a lower temperature, and the shape or size of the product is changed by regulating and controlling the process parameters, so that reference is provided for simplifying the preparation process and preparing other noble metal nano particles in a shape and size control manner, and certain guiding significance is achieved.
Disclosure of Invention
The invention overcomes the defects in the prior art, provides the dendritic PtPdCu nano particles for electrocatalytic oxygen reduction and the preparation method thereof, researches a simple and easily-repeated preparation method, prepares the dendritic PtPdCu nano particles, and not only can reduce the utilization rate of platinum but also can reduce the binding energy between the platinum and a hydrogen-oxygen bond by changing the electronic structure of the platinum so as to improve the catalytic performance of the oxygen reduction reaction.
The purpose of the invention is realized by the following technical scheme.
The dendritic PtPdCu nano particle for electrocatalytic oxygen reduction and the preparation method thereof are carried out according to the following steps:
step 1, mixing palladium salt and hydrochloric acid according to a molar ratio of (1-4): 4, uniformly mixing to obtain a palladium precursor solution, wherein the molar concentration of the palladium precursor solution is (5-20) mM;
step 2, placing 0.160g-0.450 weight part of tannic acid into a reaction container, and sequentially dripping 0.5-2.5mL of the palladium precursor solution prepared in the step 1, 0.5-16mL of copper chloride solution and 0.5-5mL of chloroplatinic acid solution into the reaction container at a dripping rate of 5-10 drops/min, and adding deionized water into the solution to obtain a mixed solution, wherein the total volume of the mixed solution is 25-35 mL;
step 3, uniformly stirring the mixed solution prepared in the step 2 at the room temperature of 20-25 ℃, transferring the mixed solution into a reaction kettle, preserving the heat at the temperature of 80-120 ℃ for 4-8h, cooling the mixed solution to the room temperature of 20-25 ℃ in a furnace cooling mode, and then cooling the mixed solution at the cooling rate of 1-5 ℃/min to obtain a black mixed solution;
and 4, centrifuging the black mixed solution prepared in the step 3, and washing the black mixed solution by using a mixture of deionized water and ethanol to obtain the dendritic PtPdCu nano particles for electrocatalytic methanol oxidation.
In step 1, the molar ratio of palladium salt to hydrochloric acid is 1: and 2, adopting 99 mass percent (59 percent of Pd%) palladium chloride powder as the palladium salt, wherein the molar concentration of the palladium precursor solution is 10 mM.
In the step 2, the dosage of the tannic acid is 0.175-0.400 part by weight, the dosage of the palladium precursor solution is 0.5-2mL, the concentration of the copper chloride solution is 5mM, the dosage of the chloroplatinic acid solution is 1-15mL, the dosage of the chloroplatinic acid solution is 1-4mL, the dosage of the chloroplatinic acid solution is 5mM, and the total volume of the mixed solution is 28-32 mL.
In step 3, stirring for 12-18min, keeping the temperature at 90-110 ℃ for 5-7h, cooling to room temperature of 20-25 ℃ in a furnace, and cooling at the rate of 2-3 ℃/min.
In step 4, the conditions of centrifugation are: the rotation speed is 15000-20000rpm, and the centrifugation time is 8-12 min.
The phase and morphology of the PtPdCu nano particles are characterized by X-ray diffraction (XRD) and a Transmission Electron Microscope (TEM), so that the dendritic PtPdCu nano particles with different components are successfully prepared, and the average size is 22-26 nm. Pt prepared by the method of example 1 was obtained from Linear voltammetry (LSV)37Pd20Cu43Nanoparticles in acidic conditions (0.1M HClO)4) Polarization curves at different rotation speeds indicate that the Pt37Pd20Cu43The nano-particles have excellent performance of electrochemically catalyzing oxygen reduction, and the oxygen reduction catalysis performance of the nano-particles prepared by the method under the acidic condition is that the average limiting current density is 0.95-1.05mA cm-2The initial potential is 920-950mV on average. From FIG. 1, it can be seen that Pt prepared by the method of example 137Pd20Cu43The nanoparticles have a face-centered cubic structure, and as can be seen from fig. 2, the morphology thereof is a dendritic core-shell structure with palladium copper as a core and platinum as a shell. As can be seen from FIG. 3, the PtPdCu nanoparticles prepared by the method are prepared under acidic conditions (0.1M HClO)4) The oxygen reduction catalytic performance of 1600r is that the limiting current density reaches 0.98mA cm-2The initial potential was 938 mV. From FIG. 4, it can be seen that Pt prepared by the method of example 232Pd16Cu52The shape of the nano-particles is a dendritic structure, and the nano-particles are slightly porous. FIG. 5 shows the Pt method in example 334Pd31Cu35The dendritic morphology of the nanoparticles is not obvious, but the size is reduced. As can be seen from FIG. 6, Pt prepared by the method of example 433Pd12Cu55The nanoparticles are agglomerated but are still small-sized, irregular core-shell structures.
The invention has the beneficial effects that: the PtPdCu nano catalyst with different components and excellent performance on electrocatalytic oxidation reduction is prepared by a one-step synthesis method which has the advantages of simple process, easy operation, easy control of the shape, the size and the good repeatability of a product; the invention also realizes the change of the product components by regulating and controlling the process parameters, which provides reference for simplifying the preparation process and controllably preparing the components of other noble metal nano-particles and has certain guiding significance.
Drawings
FIG. 1 shows Pt prepared by the method of example 137Pd20Cu43An X-ray diffraction pattern of the nanoparticles;
FIG. 2 shows Pt prepared by the method of example 137Pd20Cu43Transmission electron microscopy of nanoparticles;
FIG. 3 shows Pt prepared by the method of example 137Pd20Cu43Nanoparticles in acidic conditions (0.1M HClO)4) Polarization curve ofA wire;
FIG. 4 shows Pt prepared by the method of example 232Pd16Cu52Transmission electron microscopy of nanoparticles;
FIG. 5 shows Pt prepared by the method of example 334Pd31Cu35Transmission electron microscopy of nanoparticles;
FIG. 6 shows Pt prepared by the method of example 433Pd12Cu55Transmission electron microscopy of nanoparticles.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
1) Mixing palladium salt (palladium chloride powder with the mass fraction of 99 percent (Pd percent is 59 percent)) and hydrochloric acid (hydrogen chloride) according to the molar ratio of 1:2 to obtain a palladium precursor solution;
2) weighing 0.175g of tannic acid, sequentially dropping 1mL of 10mM palladium precursor solution, 1mL of 5mM copper chloride solution and 2mL of 5mM chloroplatinic acid solution at the dropping rate of 8 drops/min, and adding 26mL of deionized water to make the total volume of 30 mL;
3) continuously stirring the mixed solution obtained in the step 2) at room temperature for 15min, transferring the mixed solution into a stainless steel high-pressure reaction kettle, heating the mixed solution at 100 ℃ for 6h, cooling the mixed solution to room temperature in a furnace at a cooling rate of 3 ℃/min to obtain a black mixed solution;
4) centrifuging the mixed solution obtained in the step 3) for 10min at 18000rpm by a centrifuge, and washing the mixed solution by using a mixture of deionized water and ethanol to finally obtain dendritic Pt37Pd20Cu43And (3) nanoparticles.
The phase and morphology of the Pt are characterized by X-ray diffraction (XRD) and Transmission Electron Microscope (TEM), and the dendritic Pt is prepared in the embodiment37Pd20Cu43And (3) nanoparticles. The nanoparticles were obtained from linear voltammetry (LSV) under acidic conditions (0.1M HClO)4) Shows the polarization curve of the Pt37Pd20Cu43The nanoparticles have excellent performance in electrochemically catalyzing oxygen reduction.
FIG. 1 is an example1 method of preparing Pt37Pd20Cu43The X-ray diffraction pattern of the nanoparticles shows that the PtPdCu nanoparticles prepared by the method are of a face-centered cubic structure as shown in FIG. 1, and show that the PtPdCu nanoparticles are of a dendritic core-shell structure with palladium copper as a core and platinum as a shell as shown in FIG. 2. As can be seen from FIG. 3, the nanoparticles prepared by the present method were under acidic conditions (0.1M HClO)4) The oxygen reduction catalytic performance of the catalyst is that the limiting current density reaches 0.98mA cm-2The initial potential was 938 mV.
Example 2
1) Mixing palladium salt (palladium chloride powder with the mass fraction of 99 percent (Pd percent is 59 percent)) and hydrochloric acid according to the molar ratio of 1:2 to obtain a palladium precursor solution;
2) weighing 0.3g of tannic acid, sequentially dropping 1mL of 10mM palladium precursor solution, 6mL of 5mM copper chloride solution and 2mL of 5mM chloroplatinic acid solution at a dropping rate of 5 drops/min, and adding 21mL of deionized water to make the total volume of 30 mL;
3) continuously stirring the mixed solution obtained in the step 2) at room temperature for 12min, transferring the mixed solution into a stainless steel high-pressure reaction kettle, heating the mixed solution at 120 ℃ for 4h, cooling the mixed solution to room temperature in a furnace, and obtaining a black mixed solution, wherein the cooling rate is 5 ℃/min;
4) centrifuging the mixed solution obtained in the step 3) for 12min at 15000rpm by a centrifuge, and washing the mixed solution by a mixture of deionized water and ethanol to finally obtain dendritic Pt32Pd16Cu52And (3) nanoparticles.
FIG. 4 shows Pt prepared by the method of example 232Pd16Cu52As shown in FIG. 4, the PtPdCu nanoparticles prepared by the method have a dendritic structure and a few pores.
Example 3
1) Mixing palladium salt (palladium chloride powder with the mass fraction of 99 percent (Pd percent is 59 percent)) and hydrochloric acid according to the molar ratio of 1:2 to obtain a palladium precursor solution;
2) weighing 0.4g of tannic acid, sequentially dripping 1mL of 10mM palladium precursor solution, 10mL of 5mM copper chloride solution and 2mL of 5mM chloroplatinic acid solution at the dripping rate of 10 drops/min, and adding 17mL of deionized water to make the total volume of 30 mL;
3) continuously stirring the mixed solution obtained in the step 2) at room temperature for 18min, transferring the mixed solution into a stainless steel high-pressure reaction kettle, heating the mixed solution at 80 ℃ for 8h, cooling the mixed solution to room temperature in a furnace at a cooling rate of 1 ℃/min to obtain a black mixed solution;
4) centrifuging the mixed solution obtained in the step 3) by a centrifuge at 20000rpm for 8min, and washing with a mixture of deionized water and ethanol to obtain dendritic Pt34Pd31Cu35And (3) nanoparticles.
FIG. 5 shows Pt prepared by the method of example 334Pd31Cu35In the transmission electron microscope image of the nanoparticles, as shown in fig. 5, the PtPdCu nanoparticles obtained by the method of example 3 have a less pronounced dendritic morphology but a reduced size.
Example 4
1) Mixing palladium salt (palladium chloride powder with the mass fraction of 99 percent (Pd percent is 59 percent)) and hydrochloric acid according to the molar ratio of 1:2 to obtain a palladium precursor solution;
2) weighing 0.4g of tannic acid, sequentially dropping 1mL of 10mM palladium precursor solution, 15mL of 5mM copper chloride solution and 2mL of 5mM chloroplatinic acid solution at the dropping rate of 9 drops/min, and adding 12mL of deionized water to make the total volume of 30 mL;
3) continuously stirring the mixed solution obtained in the step 2) at room temperature for 16min, transferring the mixed solution into a stainless steel high-pressure reaction kettle, heating the mixed solution at 110 ℃ for 5h, cooling the mixed solution to room temperature in a furnace at a cooling rate of 3 ℃/min to obtain a black mixed solution;
4) centrifuging the mixed solution obtained in the step 3) for 9min at 17000rpm by a centrifuge, and washing the mixed solution by using a mixture of deionized water and ethanol to finally obtain dendritic Pt33Pd12Cu55And (3) nanoparticles.
FIG. 6 shows Pt prepared by the method of example 433Pd12Cu55As can be seen from FIG. 6, the PtPdCu nanoparticles prepared by the method are agglomerated, but still have a small-sized core-shell structure.
Example 5
1) Mixing palladium salt (palladium chloride powder with the mass fraction of 99 percent (Pd percent is 59 percent)) and hydrochloric acid according to the molar ratio of 1:1 to obtain a palladium precursor solution;
2) weighing 0.45g of tannic acid, sequentially dropping 0.5mL of 20mM palladium precursor solution, 16mL of 5mM copper chloride solution and 5mL of 5mM chloroplatinic acid solution at the dropping rate of 8 drops/min, and adding 13.5mL of deionized water to make the total volume 35 mL;
3) continuously stirring the mixed solution obtained in the step 2) at room temperature for 16min, transferring the mixed solution into a stainless steel high-pressure reaction kettle, heating the mixed solution at 110 ℃ for 7h, cooling the mixed solution to room temperature in a furnace at a cooling rate of 3 ℃/min to obtain a black mixed solution;
4) centrifuging the mixed solution obtained in the step 3) for 9min at 18000rpm by a centrifuge, and washing the mixed solution by using a mixture of deionized water and ethanol to finally obtain the dendritic PtPdCu nanoparticles.
Example 6
1) Mixing palladium salt (palladium chloride powder with the mass fraction of 99 percent (Pd percent is 59 percent)) and hydrochloric acid according to the molar ratio of 1:4 to obtain a palladium precursor solution;
2) weighing 0.16g of tannic acid, sequentially dropping 2.5mL of 0.5mM palladium precursor solution, 0.5mL of 5mM copper chloride solution and 0.5mL of 5mM chloroplatinic acid aqueous solution at the dropping rate of 7 drops/min, and adding 21.5mL of deionized water to make the total volume of the tannic acid to be 25 mL;
3) continuously stirring the mixed solution obtained in the step 2) at room temperature for 18min, transferring the mixed solution into a stainless steel high-pressure reaction kettle, heating the mixed solution at 100 ℃ for 7h, cooling the mixed solution to room temperature in a furnace, and obtaining a black mixed solution, wherein the cooling rate is 4 ℃/min;
4) centrifuging the mixed solution obtained in the step 3) by a centrifuge at 16000rpm for 11min, and washing by using a mixture of deionized water and ethanol to finally obtain the dendritic PtPdCu nanoparticles.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. A dendritic PtPdCu nanoparticle for electrocatalytic oxygen reduction, characterized by: the method comprises the following steps:
step 1, mixing palladium salt and hydrochloric acid according to a molar ratio of (1-4): 4, uniformly mixing to obtain a palladium precursor solution, wherein the molar concentration of the palladium precursor solution is (5-20) mM;
step 2, placing 0.160g to 0.450g of tannic acid into a reaction container, sequentially dripping 0.5 to 2.5mL of the palladium precursor solution prepared in the step 1, 0.5 to 16mL of copper chloride solution and 0.5 to 5mL of chloroplatinic acid solution into the reaction container at a dripping rate of 5 to 10 drops/min, and adding deionized water into the solution to obtain a mixed solution, wherein the total volume of the mixed solution is 25 to 35 mL;
step 3, uniformly stirring the mixed solution prepared in the step 2 at the room temperature of 20-25 ℃, transferring the mixed solution into a reaction kettle, preserving the heat at the temperature of 80-120 ℃ for 4-8h, cooling the mixed solution to the room temperature of 20-25 ℃ in a furnace cooling mode, and then cooling the mixed solution at the cooling rate of 1-5 ℃/min to obtain a black mixed solution;
and 4, centrifuging the black mixed solution prepared in the step 3, and washing the black mixed solution by using a mixture of deionized water and ethanol to obtain the dendritic PtPdCu nano particles for electrocatalytic methanol oxidation, wherein the average size of the nano particles is 22-26nm, and the nano particles are in a dendritic core-shell structure with palladium copper as a core and platinum as a shell.
2. The dendritic PtPdCu nanoparticles for electrocatalytic oxygen reduction of claim 1, wherein: in step 1, the molar ratio of palladium salt to hydrochloric acid is 1:2, the palladium salt adopts 99 percent of palladium chloride powder by mass fraction, and the molar concentration of the palladium precursor solution is 10 mM.
3. The dendritic PtPdCu nanoparticles for electrocatalytic oxygen reduction of claim 1, wherein: in the step 2, the dosage of the tannic acid is 0.175-0.400g, the dosage of the palladium precursor solution is 0.5-2mL, the concentration of the copper chloride solution is 5mmol/L, the dosage of the chloroplatinic acid solution is 1-15mL, the dosage of the chloroplatinic acid solution is 1-4mL, the concentration of the chloroplatinic acid solution is 5mmol/L, and the total volume of the mixed solution is 28-32 mL.
4. The dendritic PtPdCu nanoparticles for electrocatalytic oxygen reduction of claim 1, wherein: in step 3, stirring for 12-18min, keeping the temperature at 90-110 ℃ for 5-7h, cooling to room temperature of 20-25 ℃ in a furnace, and cooling at the rate of 2-3 ℃/min; in step 4, the conditions of centrifugation are: the rotation speed is 15000-20000rpm, and the centrifugation time is 8-12 min.
5. The preparation method of the dendritic PtPdCu nano particles for electrocatalytic oxygen reduction is characterized by comprising the following steps of: the method comprises the following steps:
step 1, mixing palladium salt and hydrochloric acid according to a molar ratio of (1-4): 4, uniformly mixing to obtain a palladium precursor solution, wherein the molar concentration of the palladium precursor solution is (5-20) mM;
step 2, placing 0.160g to 0.450g of tannic acid into a reaction container, sequentially dripping 0.5 to 2.5mL of the palladium precursor solution prepared in the step 1, 0.5 to 16mL of copper chloride solution and 0.5 to 5mL of chloroplatinic acid solution into the reaction container at a dripping rate of 5 to 10 drops/min, and adding deionized water into the solution to obtain a mixed solution, wherein the total volume of the mixed solution is 25 to 35 mL;
step 3, uniformly stirring the mixed solution prepared in the step 2 at the room temperature of 20-25 ℃, transferring the mixed solution into a reaction kettle, preserving the heat at the temperature of 80-120 ℃ for 4-8h, cooling the mixed solution to the room temperature of 20-25 ℃ in a furnace cooling mode, and then cooling the mixed solution at the cooling rate of 1-5 ℃/min to obtain a black mixed solution;
and 4, centrifuging the black mixed solution prepared in the step 3, and washing the black mixed solution by using a mixture of deionized water and ethanol to obtain the dendritic PtPdCu nano particles for electrocatalytic methanol oxidation, wherein the average size of the nano particles is 22-26nm, and the nano particles are in a dendritic core-shell structure with palladium copper as a core and platinum as a shell.
6. The method for the preparation of the dendritic PtPdCu nanoparticles for electrocatalytic oxygen reduction according to claim 5, wherein: in step 1, the molar ratio of palladium salt to hydrochloric acid is 1:2, the palladium salt adopts 99 percent of palladium chloride powder by mass fraction, and the molar concentration of the palladium precursor solution is 10 mM.
7. The method for the preparation of the dendritic PtPdCu nanoparticles for electrocatalytic oxygen reduction according to claim 5, wherein: in the step 2, the dosage of the tannic acid is 0.175-0.400g, the dosage of the palladium precursor solution is 0.5-2mL, the concentration of the copper chloride solution is 5mmol/L, the dosage of the chloroplatinic acid solution is 1-15mL, the dosage of the chloroplatinic acid solution is 1-4mL, the concentration of the chloroplatinic acid solution is 5mmol/L, and the total volume of the mixed solution is 28-32 mL.
8. The method for the preparation of the dendritic PtPdCu nanoparticles for electrocatalytic oxygen reduction according to claim 5, wherein: in step 3, stirring for 12-18min, keeping the temperature at 90-110 ℃ for 5-7h, cooling to room temperature of 20-25 ℃ in a furnace, and cooling at the rate of 2-3 ℃/min.
9. The method for the preparation of the dendritic PtPdCu nanoparticles for electrocatalytic oxygen reduction according to claim 5, wherein: in step 4, the conditions of centrifugation are: the rotation speed is 15000-20000rpm, and the centrifugation time is 8-12 min.
10. Use of the dendritic PtPdCu nanoparticles for electrocatalytic oxygen reduction as claimed in any one of claims 1 to 4 in the preparation of an electrocatalytic oxygen reduction catalyst, wherein: the oxygen reduction catalytic performance of the dendritic PtPdCu nano particles under the acidic condition is that the average limiting current density is 0.95-1.05mA cm-2The initial potential is 920-950mV on average.
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